Flowable hectographic compositions

ABSTRACT

Flowable colored compositions containing alkoxylated fatty acid alkanolamides as viscosity stabilizers. The compositions preferably contain up to about 20% by weight of the reaction products of ethylene oxide with monoethanolamides of higher fatty acids and are particularly suitable for the preparation of hectographic papers.

United States Patent Riedel et a1.

FLOWABLE HECTOGRAPHIC COMPOSITIONS Inventors: Guenther Riedel, Heidelberg; Rudolf Waechter, Limburgerhof, both of Germany Assignee: Badische Anilin- & Soda-Fabrik Aktiengesellschaft, Ludwigshafen/Rhein, Germany Filed: Nov. 14, 1972 Appl. No.: 306,437

Foreign Application Priority Data Nov. 16, 1971 Germany ,1 2156762 US. Cl 106/145, 106/21, 106/22, 106/27, 106/31, 106/32, 106/308 N,

Int. Cl. t. C09k 3/00, C09d 1 1/06 Field of Search 106/145, 21, 22, 308 N, 106/290, 308 F, 308 Q, 32, 288 B, 27, 31; 117/356; 252/357; 260/459 R Primary ExaminerJoseph L. Schofer Assistant Examiner-T, S. Gron Attorney, Agent, or Firm-Johnston, Keil, Thompson & Shurtleff [57] ABSTRACT Flowable colored compositions containing alkoxylated fatty acid alkanolamides as viscosity stabilizers. The compositions preferably contain up to about 20% by weight of the reaction products 011 ethylene oxide with monoethanolamides of higher fatty acids and are particularly suitable for the preparation of hectographic papers.

8 Claims, N0 Drawings sesame 1 Nov. 26, 11974 FLOWABLE HECTOGRAPHIC COMPOSITIONS This invention relates to colored inks containing alkoxylated fatty acid alkanolamides for hectographic purposes.

ln the manufacture of hectographic compositions the dyes are dispersed in a wax composition with the aid of grinding equipment. The resulting hectographic compositions are transferred, in the molten state, to tanks from which they are applied to a paper by, say, a printing or knife-coating technique. Hectographic papers of this kind may then be used for making copies in a simple manner by transfer printing.

During storage and processing of hectographic compositions in the liquid state, a considerable increase in viscosity frequently occurs. Before the coating operation commences or is complete the compositions become so thick that the production rate must be reduced considerably. When stored forv long periods, the compositions stiffen irreversibly and thus become useless for coating operations.

We have now found that hectographic compositions remain stable and flowable on storage when they contain alkoxylated fatty acid alkanolamides in a concentration of from 1 to by weight based on the total weight of the composition.

The alkoxylated fatty acid alkanolamides used as additives in the hectographic compositions of the invention are fatty acid amides containing oxyalkyl groups, preferably obtained by alkoxylating fatty acid alkanolamides. Of said fatty acid alkanolamides, the ethanolamides and in particular the monoethanolamides are especially preferred. Particularly suitable fatty acids are the higher fatty acids or mixtures thereof such as palmitic acid, stearic acid, oleic acid, tallow fatty acid, coconut fatty acid and similar acids. The fatty acid alkanolamides are reacted with alkylene oxides, preferably ethylene oxide. The molar ratio of fatty acid alkanolamide to alkylene oxide in this reaction is conveniently from 1:5 to 1:25 and preferably from 1:8 to 1:15.

The alkoxylated fatty acid alkanolamide is incorporated in the hectographic composition of the invention in an amount of from 1 to 20% and preferably from 2 to 10% by weight before, during or after the dye component has been ground together with the wax component for dispersion therein. Alternatively, the alkoxylated fatty acid alkanolamide may be added to the dye component during its manufacture or during milling thereof, or it may be added to the wax component before this is mixed with the dye. Where the said alkoxylated alkanolamide is added to the dye during its preparation, it has been found particularly advantageous to stir the alkoxylated alkanolamide into the watercontaining melt of the dye and then dry the mixture.

The dye component forms the major component of the hectographic composition, usually being present therein in an amount of from to 60% by weight based on the total weight of the composition, and suitable dyes for use in the present invention are all conventional hectographic dyes, particularly triarylmethane dyes such as Crystal Violet (C.l. No. 42,555), Methyl Violet (C.l. No. 43,535) and Victoria Blue B (C.l. No. 44,045), as well as mixtures of said dyes.

Suitable waxes for use in the hectographic composition are any of the usual natural and synthetic waxes and oils such as carnauba wax, lanolin, Vaseline, paraffin wax, ozocerite, beeswax, montan waxes crude or modified (ester wax), mineral oils, paraffin oil. ma-

chine oil, spindle oil, neats foot oil, bone oil, peanut oil, castor oil, sunflower oil, rapeseed oil, poppy seed oil and olein, either alone or in the form of mixtures.

The hectographic compositions of the invention remain stable and flowable when stored for long periods and when subjected to the elevated temperatures normally used in further processing and they are thus eminently suitable for coating hectographic papers. Although other non-ionic emulsifiers are used in order to reduce the hardness of diand tri-arylmethane dyes and thus to make such dyes more suitable for hectographic applications, such emulsifiers have no or no appreciable viscosity stabilizing effect in hectographic compositions. It is therefore surprising that the group of alkoxylated fatty acid alkanolamides, when added to hectographic compositions essentially consisting of a dye component and a wax component, cause the flowability of the said compositions to be maintained under conditions of storage and elevated temperatures and are therefore to be regarded as viscosity stabilizers.

The invention is further illustrated with reference to the following Examples in which the parts are by weight.

EXAMPLE 1 354 Parts of moisture-containing Crystal Violet (solids content 200 parts) are melted over a water bath to form a solution. 10 Parts of reaction product of 1 mole of oleic monoethanolamide and 10 moles of ethylene oxide are stirred into said solution. The composition is stirred and the water evaporated therefrom until it stiffens, whereupon it is dried in a vacuum drying cabinet at C until the moisture level is only about 2%. The resulting lumps are milled to a dye powder which is suitable for incorporation in hectographic compositions such as is described for example in Example 4.

EXAMPLE 2 20 Parts of a reaction product of 1 mole of tallow fatty acid monoethanolamide (monoethanol mixture obtained from an acid mixture of 47% of oleic acid, 29% of palmitic acid, 18% of steariic acid, 3% of myristic acid and 3% of linoleic acid) and 12 moles of ethylene oxide are homogeneously mixed with 30 parts of water and then stirred into 354 parts of a dye melt as described in Example 1, the resulting mixture being further processed as described in Example 1. There is obtained a Crystal Violet dye composition suitable for incorporation in a hectographic composition as described in Example 5 for example.

EXAMPLE 3 300 Parts of Crystal Violet (solids content parts) and 60 parts of Methyl Violet (solids content 30 parts) are melted over a water bath and mixed with 25 parts of a reaction product of 1 mole of oleic ethanolamide and 10 moles of ethylene oxide. The mixture is processed as described in Example 1 to give a dye composition having a moisture content of about 3%.

EXAMPLE 4 144 Parts of a wax mixture consisting of 36 parts of carnauba wax, 36 parts of Vaseline, 51 parts of lanolin and 21 parts of mineral oil are ground together with 156 parts of Crystal Violet dye powder as obtained in Example 1 using 600 parts of steatite spheres in a stirred ball mill at 95C, the speed of rotation being 800 rpm. After 90 minutes, the resulting hectographic compositionis removed from the spheres and its viscosity is measured in an Epprecht viscometer (measuring system B, velocity stage I) at 95C immediately and during a storage period of 24 hours. The test results show an initial viscosity of 580 centipoise, which does not change in the course of 24 hours. A control dye composition not containing the ethoxylated oleic monoethanolamide shows an initial viscosity of 700 centipoise which rises in the course of 24 hours at 95C to 1,500 centipoise.

EXAMPLE 5 The Crystal Violet dye composition obtained in Example 2 is ground together with a wax composition in a stirred ball mill following the procedure described in Example 4. Viscosity measurements show an initial viscosity of from 520 to 550 centipoise at 95C, the viscosity remaining at this level throughout a storage period of 24 hours at 95C.

EXAMPLE 6 48 Parts of a wax mixture consisting of 12 parts of carnauba wax, 12 parts of vaseline, 17 parts of lanolin and 7 parts of mineral oil are ground together with 52 parts of the dye composition obtained in Example 1 on a three-roll mill, the mixture being passed through the mill 4 times at room temperature and a pressure of 60 atmospheres gage and twice at 95C at a pressure of from 10 to atmospheres gage. The viscosity of the hectographic composition thus obtained is the same after storage for 4 days at 95C as before storage, i.e. 370 centipoise. The control dye composition prepared without said ethoxylation product shows a rise in viscosity over the said period of from 480 to 1,500 centipolse.

EXAMPLE 7 13 Parts of carnauba wax, 17 parts of vaseline, 13 parts of bone oil, 2 parts of oleic acid and 55 parts of Crystal Violet are ground together with 2.75 parts or 5 parts or 10 parts of a reaction product of 1 mole of tallow fatty acid monoethanolamide and 12 moles of ethylene oxide in the three-roll mill as described in Example 5. Viscosity measurements of the resulting hectographic composition give initial values of 510, 440 and 370 centipoise at 95C respectively, these values not changing over a storage period of 24 hours at 95C. The corresponding composition not containing the ethoxylation product shows an initial viscosity of 1,100 centipoise and values above 2,000 centipoise after storage for 24 hours at 95C.

EXAMPLE 8 354 Parts of moisture-containing Crystal Violet (solids content 200 parts) are melted over a water bath to form a solution. 4 parts of a reaction product of l mole of oleic monoethanolamide and 10 moles of ethylene oxide are stirred into said solution. Further treatment of the composition is as described in Example 1. 156 Parts of the resulting Crystal Violet dye powder are ground together with 144 parts of a wax mixture consisting of 36 parts of carnauba wax, 36 parts of vaseline, 51 parts of lanolin and 21 parts of mineral oil, as described in Example 4, to form a hectographic composition. Viscosity measurements carried out in the manner described above give an initial viscosity of 600 centipoise at C, this showing no change over 24 hours.

EXAMPLE 9 354 Parts of moisture-containing Crystal Violet (solids content 200 parts) are melted over a water bath to form a solution. 40 Parts of a reaction product of 1 mole of oleic monoethanolamide and 10 moles of ethylene oxide are stirred into said solution. Further treatment of the composition is as described in Example 1. 156 Parts of the resulting Crystal Violet dye powder are ground together with 144 parts of a wax mixture consisting of 36 parts of carnauba wax, 36 parts of Vaseline, 51 parts of lanolin and 21 parts of mineral oil as described in Example 4 to provide a hectographic composition. The viscosity measurements carried out as described above give an initial viscosity of 500 centipoise at 95C, this showing no change over 24 hours.

We claim:

1. A flowable hectographic composition consisting essentially of (a) a hectographic dye, (b) a wax and (c) as a viscosity stabilizer an alkoxylated fatty acid alkanolamide in a concentration of from 1 to 20% by weight ofthe total weight of the hectographic compositron.

2. The flowable hectographic compositions as claimed in claim 1, wherein the alkoxylated fatty acid alkanolamides used are reaction products of ethylene oxide with monoethanolamides of higher fatty acids.

3. A composition as claimed in claim 1 wherein the concentration of said alkoxylated fatty acid alkanolamide is about 2 to 10% by weight.

4. A composition as claimed in claim 1 wherein the hectographic dye is present in an amount of about 30 to 60% by weight based on the total weight of the composition.

5. A composition as claimed in claim 1 wherein said dye is a triarylmethane dye.

6. A composition as claimed in claim 1 wherein said wax is a substance selected from the class consisting of natural and synthetic waxes, mixtures thereof, and admixtures thereof with oils.

7. A composition as claimed in claim 1 in which the molar ratio of the fatty acid alkanolamide to the alkylene oxide is about 1:5 to 1:25.

8. A composition as claimed in claim 1 in which the molar ratio of the fatty acid alkanolamide to the alkylene oxide is about 1:8 to 1:15. 

1. A FLOWABLE HECTOGRAPHIC COMPOSITION CNSISTING ESSENTIALLY OF (A) A HECTOGRAPHIC DYE, (B) A WAX AND (C) AS A VISCOSITY STABILIZER AN ALKOXYLATED FATTY ACID ALKANOLAMIDE IN A CONCENTRATION OF FROM 1 TO 20% BY WEIGHT OF THE TOTAL WEIGHT OF THE HECTOGRAPHIC COMPOSITION.
 2. The flowable hectographic compositions as claimed in claim 1, wherein the alkoxylated fatty acid alkanolamides used are reaction products of ethylene oxide with monoethanolamides of higher fatty acids.
 3. A composition as claimed in claim 1 wherein the concentration of said alkoxylated fatty acid alkanolamide is about 2 to 10% by weight.
 4. A composition as claimed in claim 1 wherein the hectographic dye is present in an amount of about 30 to 60% by weight based on the total weight of the composition.
 5. A composition as claimed in claim 1 wherein said dye is a triarylmethane dye.
 6. A composition as claimed in claim 1 wherein said wax is a substance selected from the class consisting of natural and synthetic waxes, mixtures thereof, and admixtures thereof with oils.
 7. A composition as claimed in claim 1 in which the molar ratio of the fatty acid alkanolamide to the alkylene oxide is about 1:5 to 1:25.
 8. A composition as claimed in claim 1 in which the molar ratio of the fatty acid alkanolamide to the alkylene oxide is about 1:8 to 1:15. 